Copolymers of 2-phenyl allyl and acrylo materials



United States Patent 3,230,205 COPOLYMERS 0F Z-PHENYL ALLYL AND ACRYLO MATERIALS Willis C. Keith, Lansing, 111., assignor to Sinclair Research, Inc., Wilmington, DeL, a corporation of Delaware No Drawing. Filed Dec. 1, 1961, Ser. No. 156,497

14 Claims. (Cl. 260-855) This invention concerns novel copolymers of Z-phenylallyl alcohol, its esters and ethers, vw'th acrylo materials; viz, acrylonitrile and acrylate esters. These polymers are solids at ambient temperatures and have properties which make them useful for a number of applications. They make excellent protective coatings, are resistant to most organic solvents and to scratching and adhere tenaciously to polar surfaces such as glass. They are transparent, and. thus can be used to coat decorative items.

One of these polymers, that formed from 2-pheny-l-allyl alcohol and acrylonitrile has the remarkable property of changing its characteristics when heated for a short time at relatively low temperatures. Ordinarily this polymer can be produced at about 5060 C. to produce a solid polymer which is soluble in solvents such as acetone, but when products, for example, films, prepared at low temperatures are cured in the absence of an initiator or catalyst, the polymer becomes insoluble in all common organic solvents. Thus, the alcohol-nitrile polymer is characterized by different properties in the uncured and cured state. Infrared data indicate that this change is at least to some extent a chemical change. In either state this polymer as well as the others, has excellent optical properties, being transparent and highly glossy.

In the uncured state, the alcohol-nitrile polymer is effective as a bonding or sealing agent. The novel copolymers of this invention are characterized by an intrinsic viscosity of about 0.1 to 2, preferably about 0.15 to 1.6 in dimethyl formamide at 37.8" C. and all but the cured alcohol-nitn'le polymer are thermoplastic. [Intrinsic viscosity is calculated by extrapolating to zero the measured specific viscosity of several solutions of the polymer in the solvent at less than 2% polymer concentration.

It is of interest, as well as a novel part of this invention, to note that the crude polymers can be used for the preparation of coatings without the usual purification procedures that are commonly used to remove low molecular weight polymers as well as reaction initiators that may be detrimental to film properties.

Acrylate polymers included in this invention are im proved over conventional acrylate polymers; for example, methyl methacrylate polymers ordinarily possess excellent optical properties but are soft and are not scratch resistant, making them unsatisfactory for many applications. A major difficulty encountered in preparing acrylate polymers is avoiding run away polymerization resulting in poor physical properties of the polymers. When acrylates are copolymerized with 2-phenyl-allyl alcohol, the polymers are very hard and for the most part are scratch resistant, the extent of this property being somewhat dependent on polymer composition as well as conditions that are used for the polymerization reaction and presumably crosslinking that may take place during the curing operation. In addition to the improved properties of the polymers, the Z-phenyl-allyl alcohol serves as a moderator for the polymerization reaction, preventing the run away that results in poor physical properties of the polymers.

The composition of the copolymers can be varied over a wide range, the end usage dictating the optimum composition. For most uses the combining weight ratio is 0.001 to 20 parts allyl material to one part acrylo madeleteriously afiect the reaction.

terial. For the copolymers of acrylonitrile and 2-phenyl-' allyl ester or ether, the preferred proportions are 0.05 to 3 parts allyl ester or ether to 1 part acrylonitrile. For the copolymer of 2-phenyl-allyl alcohol with acrylates the preferred proportions are 0.001 to 3 parts allyl alcohol to 1 part acrylate. For the copolymer of Z-phenylallyl alcohol and acrylonitrile the preferred proportions are about 0.1 to 9 parts allyl alcohol to one part acrylo, with the ratio for coatings and films with the most desirable spectrum of qualities being about (M5 to 4 parts 2- phenyl-allyl alcohol to one part by weight of acrylonitrile. In this range, the polymer has the best hardness, transparency and clarity. Fractionation of the non-heat treated polymer product shows a substantially uniform heteropolymer is formed at any proportions within the ranges recited above, rather than a mixture of homopolymers.

The 2-phenyl allyl starting material for the copolymers of this invention is of the type H n d=o -o a 1 1 I I where R is hydrogen, hydrocarbon (alkyl, aryl, etc.) or acyl (including aromatic acyl), generally of 1-8 carbon atoms and R is hydrogen, halogen, or a hydrocarbon radical of 1-l0 carbon atoms, for example alkyl or fusedring hydrocarbon radicals such as naphthyl. The acrylo component has the configuration where R is as defined above and Y is cyano or COOR where R is alkyl of 1-6 carbon atoms. Any of the R groups may be substituted with substituents that do not Preferably R, when a hydrocarbon, is methyl or ethyl and R is 'methyl.

2-phenyl-allyl alcohol may be made by suitable methods, for example, as disclosed in US. Patent 2,537,622, and esters may be prepared from this by known reactions with suitable acids. The ether may be prepared by refluxing the allyl chloride with an alkali alcoholate of the ROI-I alcohol.

It is preferred that the polymerization reaction be carried out by dissolving the allyl and acrylo materials in the proper proportions in a so-called ideal solvent; that is, one in which all of the reactants and the polymer product are soluble. Such an ideal solvent is dimethyl formamide. Non-ideal hydrocarbon solvents such as cyclohexane and benzene, which dissolve the monomers but precipitate the polymers, may also be used, and, actually, bulk polymerization, in which the reactants are contacted in the liquid state without a solvent, is satisfactory under certain conditions; for example, it is generally advisable to prevent curing of the allyl alcohol-nitrile polymer until it has been given its final form and to prevent long exposure to relatively high temperatures which could cause other polymers, such as those containing acetate, to cross-link to an infusable material or a material insoluble in ordinary solvents. Emulsion polymerization is also sometimes feasible. The monomers are usually charged to the reactor at the same time, however the addition of the allyl material to molding syrups (partially polymerized acrylates) that are frequently used gives satisfactory results, and in some cases this is the preferred procedure.

The polymerization reaction is carried out by the use of free radical initiators such as peroxides, azocompounds, etc. The quantity of initiator employed is not of prime importance; however, the reactions run well employing from about 0.5 to weight percent peroxide as benzoyl peroxide. 'Ilhe use of gamma rays, for extial insolubility toward acetone and dirnethyl tormamide which are representative organic solvents. films, or articles coated With the polymer, may, for in-- stance, be treated for several hours at about 65 to 75 C.-

ample, from cobalt-60, to promote the polymerization 5 to give the desired effect or for one hour or less at aboutreaction has been successful and is considered to be a 100 C. or for a few minutes up to about an hour ati source for the production of free radicals. Redox catabout 130 C. This second stage product is highly de-- alyst systems are also included within the scope of this sirable for many applications, but is not necessary in invention. many instances.

The polymerization may be carried out at a tempera- 1O EXAMPLES ture within the range of about 0 to 100 C., but for high molecular weight polymers it is best to restrict the reach tollowlhg eXe-mples are tnusthatllfe h this ti n temperature t b l b t 60 of 65 C t i i. ventron but are not to be considered lll'llltlllg Each mize chain transfer reactions. When the phase-change- 0t EXampleS Was P Y shhlstahtlelly the able copolymer of 2-phenyl allyl alcohol and acrylonitrile Same e The hqhld reagents Sohltlohs of is made, temperatures above about 65 C. may be used reagents 1h benzene Il-heXehe eyelolhexehe and such a procedure may accomplish both first stage d1h1ethy1 tetm'amlde Were charged to pe y (polymerization) and second stage (curing) treatments e tubes Whleh e evacuated e flushed Wlth P if the reaction initiator or catalyst is removed, destroyed n1trogen f sevefalhhllllltes t0 eh-mlhate Oxygen e or deactivated after sufiicient polymerization has 00- e Teaetloh- A POsltlve Pressure of hltrogeh Wee malncurred. The most desirable lower polymerization temtamed 011 tubes y means of a hallOOh- The tubes p t i b ut C Th tio i ll run were allowed to warm to room temperature and then at about 56 C. for a period of several hours. There Placed in a Constant temperature bath the time and are no special pressure requirements, but the liquid phase temperature llldleated In Tables V h VI belowshould be maintained and the pressure kept constant dur- 25 The P ly were worked D y eohvehttohal P ing the reaction. At least about 75%, preferably about t y, P Y e e dlSSOlVed 111 e'h s 0 8085 percent, of the monomers is ordinarily converted dlmethyl formamlde and p t e y the addltloll of to polymer when the reaction is run to give what appears Where. all ye 1S glveh, the P y to be the most desirable copolyrner. However, the re- Were a y y Infrared, 'g 0r eehheh'hydrogeh action can be carried essentially to completion by allowanalyslsing the reaction to continue for several hours (288) at Table I p 9 eoPolymers of -p y y alco- 25 c. or for a much shorter time at 100 c. (4 hours). 1 and acrylomtrlle- All the polymers were o ub e With the allyl alcoho-l-acrylonitrile polymerization 1n DMF 311d acetone eXeePt the gl'ems ffaetlon of solvent removed, this solid copolymer may be shaped to Exampl and the P Odhet of Example The Solutloht d i d f rm. Alternatively, films of any of the precipitatron procedure was repeated several times and copolymers of this invention may be prepared from a finally the polymers were dried in a vacuumoven at dilute, say about 10%, solution of the polymer in an below 65 C.

Table I Monomers Catalyst, Conditions Polymer Example benxoyl Solvent Number perozide (g) (ml) Alcohol Nitrile Temp., Time, Yield W7 percent Wt. percent (g) (g.) 0. hrs. (g.) Nitrile Alcohol 2.0 2.4 0.04 None 56 10 2.0 2.0 2.4 0. 05 (1) 10.0 50 70 2.5 0.5 3.6 0.125 (1) 10.0.- 50 24 3.3 1.0 3.2 50 24 2.0 0.40 56 72 0.3 2.0 2.40 50 24 0.8 0.25 3.8 56 is 3.5 2.0 2.4 50 1 24 2.3 2.0 2.4 50 24 2.16 2.0 2.4 50 24 3. 40 2.0 2.4 1 24 3. 07 2.0 2.4 50 24 2. 70 2.0 2.4 50 1 24 3.54

ideal solvent such as dimethyl for-mamide by casting and removing the solvent at about 100 C. and 375 mm. Hg absolute pressure.

The curing, reforming, or further chemical conversion of the 2-phenyl-allyl alcohol-acrylonitrile copolymer takes place at a temperature of about to 130 C. in the substantial absence of the polymerization initiator. Also, usually, this treatment is conducted in the substantial absence, of solvent. Curing takes place at a temperature greater tha about 65 C. but not so high as to destroy the polymer, the time depending upon the temperature chosen. In any event, the heat treatment is prolonged for the time necessary to produce substanwherein N is the viscosity index, N is the specific The polymer" viscosity, c is the concentration, i.e., grams of polymer/ 100 ml. of solution, T is the flow time of the polymer solution in seconds and 231.9 is the flow time of the solvent alone. The viscosity index is generally numerically equivalent to the intrinsic viscosity.

These examples illustrate a number of significant variables that have an effect on the alcohol-nitrile reaction as well as the polymer that it produced. Examples number 1, 3 and 15 illustrate that the composition of the polymer can be varied over a wide range by employing various ratios of 2-phenyl-allyl alcohol to acrylonitrile. A comparison of these examples also illustrates that the quantity of initiator can be varied over a wide range and does not appear to be critical. The following examples taken from Table I illustrate the effect of solvent on the reaction as indicated by the yield of polymer.

Example Solvent Percent conversion to polymer 12 None 63 Benmne 49 Cyclohexane 79 Dimethyl iormamidemufi- 81-83 The following examples are used to illustrate the efiect of polymer composition on film properties. The films were prepared from a percent solution of allyl alcoholacrylonitrile copolyrner in dimethyl formamide. The solvent was evaporated at 100 C. and 375 mm. Hg absolute, destroying any free radical materials and forming thin films.

Composition Example Properties Number Wt. Percent Alcohol Wt. Percent N itr ile 87 13 Film was clear-transparent,

The film described in Example 20 possesses excellent properties but is definitely inferior to the film described in Example 21, and the film used for Example '22 was very poor compared to the other films. The optical and bonding properties of the polymers are definitely poor when these polymers contain over about nitrile.

EXAMPLES 23 AND 24 A polymer was prepared identical to the one illustrated in Example 19, and the uncured, crude polymer was diluted to 10 percent by the addition of dimethyl formamide. The polymer solution was divided into two equal parts. One part was used for the preparation of films without out any purification, and the other part was treated with methanol to precipitate the polymer. The precipitated polymer was dissolved in acetone and reprecipitated by the addition of methanol. This procedure was repeated three times and the polymers were dissolved in dimethyl formamide for the preparation of films. Films from both the crude and purified polymer were prepared by removing the solvent at C. and 375 mm. of Hg absolute.

Polymer Properties Purifled Film was very hard (scratch resistant),

transparent and adhered tenaciously to glass.

Film appeared identical to the film prepared from the polymer that was purified by precipitation (Example 23) Crude EXAMPLES 2838 Table III Polymer Film treated Example wt. percent Solvent at 25 C. Time (hrs) Loss Number co (wt. percent) Time (hrs) The high purity -phenyl-allyl alcohol was prepared EXAMPLES 49-58 A near quantitative yield was obydrolysis reaction.

The ethyl ether of 2 by refluxing 2-phenyl-allyl chloride in 90% ethanolic alkali for 24 hours.

2-phenyl-allyl-ethyl ether boiled at 96 C. at 10 mm. and a refractive index of n =1.5202 was obtained.

Table IV u 366 finis dis mm m mmudm m mm 235 M0 01121002123 U0 F m awmm TM d .m t M S I f eh Y/\ a W0%640 d mo k D h V uU D 6 M 1 ssLLssssssL M w a s Pw M w m P... m 0 2 m F ht S OOPX 1 t e d \J n w m m wmw m 7m mm e 3618664938 SSSSSSSSSSS V. m m Mk d m d 00 0 0 4 L2LL3LL0 sm m e efim Emd m v. a e we m B L V. CHW u m. m mm S weadn mm n Z y S y mm W. m m m ud em u B SIIIIISI f m K n W Sm 5 a r. 6666062272733 m W18 0. E m mm a m 44442299 2255 .1 m K M P M L w am m m h, w M mm m mmw mxfl M m m D SIIISSSI t m m e r 11 a 1 n en xd he o e 0 CE w E W h 0 m m pm 1 6666666666666 P PM 6 1 OT h a a e a C 5555555555555 .1 u P n B xx E fl. N S n amEEs Sw m r d .S-.1 r 1 9 mm a. mama; 5 m m m mm M be... main wmm T e e t O W1 m. I \J 000000000000 em Y O S p m O 1W. V g 111111111111 P km v mm m mflu W .h WM uaaaaaaaaaaao 10a 8 e leteh en e Z0 M m Mau ham? Rh 1 mm w w mw r nm m am 5 H .m 0 fe5 0 m r Bu m Tfl w W V s T@ CEofl5WP.m.m 20 T u. .1 m a k m e m e m m. mmmmmmwwmw m mmwmwmweww t .t m). 0 g o d e 1 m. o p. hw wm nwhmmme Wm T c we mm mm m .m S a T mam ms d m a m n m mw mmmm J v. t h e J 0. m m f; ae a m m .m( 1 0 a mam w 0 Del W e a 443244324 s m f hm m t tem m m m A A AA 4145 2 s 0( d n .pvcmc e mMmMmwumm AA 0 n s a m .mce m d m MMMMMMMMMMMMM 1e 1 u a t cs n 1 Yd S b n adEd a M mm) 0 00 m 1,6 m .mw m S C W 5000500055000 m m 4 WW 0 m K m w fl fi araaaraaaurzs h 9 n m e m v. orm h a l r. I 1 c 3 a m C O a O uh o m S 5 BD. a D a -.V.I..HSW..H M n 4 268448444 E w lvfl 21 V H d C A e e .1 t M 2 331023222 L .U S 500000050 0 IN; E m m a m H mm m m Rw P .m m m) eavaaaaaees w m a d c N M n u ev M A w m Wmm mm m mwwm d mm X e R 6V.S 210 rdD e 005000%000 Eh dS .flm m m w w m t f t p U e l pfi p S EN h 2 103220222 S 500000050 0 t M t a m b a W 3 WW W m) 0 L2 2 &L20 L2 m wmamwtmmmmmfle f A a m .1 m em n mm r 7 m w v m m mmw% 1 we d 6 II" mw mmTa e e,m r mm I a me E: mm mw mamw www n a m n t l C MN I T m E: wm m wmmia mmm w m E meme esnk PfihHmEnEp.

In none of the above examples was a loss in weight observed and the films retained their excellent properties.

An increase in Weight was observed with both acetone and methanol as indicated in Examples 37 and 38 but no other change in the film Was observed. Thus the excellent 5 mi d fro h h resistance of the alcohol-nitrile copolymers of this invention to various solvents is apparent.

Of these solid polymers, those of Examples 59 to 62 were white powders which could be transformed to transparent films with excellent bonding properties. These copolymers, as well as Samples 64 to 67 were soluble in acetone, from which they could be precipitated by methanol. These latter copolymers formed transparent plastics that were very hard and scratch resistant. The same properties inhered in Example 63, except that only 10% of this polymer dissolved in acetone at 56 C. for 48 hours. The copolymer of Example 68 adhered tenaciously to glass upon melting and was clear and transparent. The polymer of Examples 70 and 71 dissolved in DMF and films prepared at 100 C. (375 mm. Hg) were hard and scratch resistant.

The following experiments were run in cells prepared from plates of Pyrex glass having the dimensions of x 5 inches and about A of an inch thick. A Teflon O ring was clamped between two pieces of this glass and a small hole was provided in the top side for filling. After the molds were filled the opening was sealed oflf, after the removal of air.

EXAMPLE 72 Ten grams of methyl-methacrylate containing 0.10 g. of benzoyl peroxide was charged to the glass cell. The cell was heated for hours at 58 C., then 12 hours at 60 C. and finally for four hours at 100 C. The cell was cooled to about 60 C., the clamps removed and placed in cool water (about 20 C.) and the sheet of polymer separated from the glass.

EXAMPLE 73 A copolymer was prepared by charging 9.5 grams of methyl methacrylate and 0.5 gram of 2-phenyl-allyl alcohol containing 0.10 gram of benzoyl peroxide to the cell described in the previous example. The same heating schedule was also employed. A comparison of the two polymers showed a definite improvement in the hardness of the polymer containing Z-phenyl-allyl alcohol. The polymer also possessed excellent optical porperties typical of acrylate polymers.

EXAMPLE 74 A copolymer was prepared by charging 9.0 grams of methyl-methacrylate and 1.0 gram of 2-phenyl-allyl-alco hol containing 0.10 gram of benzoyl peroxide to the cell. The same heating schedule was used as described in Example 72. The polymer produced in this experiment was very hard, scratch resistant, and possessed excellent optical properties. This polymer was a considerable improvement over the polymer described in Example 72.

It is claimed:

1. A solid copolymer containing about 0.001 to 20 parts of an allyl material of the type where R is selected from the group consisting of hydrogen, hydrocarbon of 1-8 carbon atoms and acyl of 1-8 carbon atoms, per part of a second material of the type Where R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1-10 carbon atoms and Y is selected from the group consisting of cyano and COOR where R is alkyl of 16 carbon atoms, said copolymer being made by polymerization using a free radical initiator.

2. The copolymer of claim 1 characterized by an intrinsic viscosity of 0.1 to 2 in dimethyl formamide at 37.8" C.

3. The copolymer of claim 1 in which the second material is acrylonitrile.

4. The copolymer of claim 3 in which the allyl material is 2-phenyl-allyl acetate.

5. The copolymer of claim 3 in which the allyl material is 2-phenyl-allyl ethyl ether.

6. The copolymer of claim 1 in which the allyl material is 2-phenyl-allyl alcohol and the second material is methyl acrylate.

7. A polymer of Z-phenyl-allyl alcohol and acrylonitrile containing about 0.0001 to 20 parts by weight of 2-phenylallyl alcohol to one part of acrylonitrile, characterized by an intrinsic viscosity of about 0.1 to 2 in dimethyl formamide at 37.8 C. and being made by polymerization using a free radical initiator.

8. The polymer of claim 7 containing about 0.1 to 9 parts by weight of alcohol to one part of acrylonitrile.

9. A solid polymer of Z-phenyl-alkyl alcohol and acry lonitrile characterized by insolubility in dimethyl formamide and acetone, containing about 0.001 to 20 parts by weight of Z-phenyl-allyl alcohol to one part of acrylonitrile and being made by polymerization using a free radical initiator and curing the resulting polymer.

10. The method of claim 14 in which the initiator is benzoyl peroxide.

11. The method of claim 14 in which the polymerization temperature is about 25 to C.

12. The method of claim 14 in which the polymerization mixture contains a solvent for the reactants.

13. The method of claim 12 in which the uncured polymer is also soluble in the solvent.

14. A method for making a polymer of 2-phenyl allyl alcohol and acrylonitrile characterized by insolubility in acetone and dimethyl formamide which comprises polymerizing said alcohol and said nitrile in a ratio of about 0.001 to 20 parts by weight of said alcohol to one part of said nitrile in the presence of a free-radical initiator at a temperature of about 0 to C. and curing the resulting polymer by holding it in the absence of free-radical material at a temperature of about 65130 C. for a time sufiicient to bring about said insolubility characteristics.

References Cited by the Examiner UNITED STATES PATENTS 2,455,722 12/1948 Adelson et a1 260-913 2,537,622 1/1951 Butler 26091.3 2,624,722 1/ 1953 Kropa et al. 260-855 3,065,198 11/1962 Abramo et al. 260-855 JOSEPH L. SCHOFER, Primary Examiner. LOUISE P. QUAST, DONALD E. CZAJ A, Examiners. 

1. A SOLID COPOLYMER CONTAINING ABOUT 0.001 TO 20 PARTS OF AN ALLYL MATERIAL OF THE TYPE 